This invention relates to melt processible perfluorocarbon resin compositions containing degradation retarders. More particularly it relates to such compositions of zeolites and a copolymer of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) known as FEP, a copolymer of TFE with perfluoropropylvinyl ether (PPVE) known as PFA, and a terpolymer of TFE, HFP and PPVE.
Various materials have been found to be useful in retarding the degradation of many polymer systems upon exposure to be elevated temperatures or to radiaion, particularly ultraviolet light. Often oxygen from the air enhances degradation.
Organo-sulfur compounds and various organo-metallic compounds and hindered amines are used to retard degradation of polymers meant to be used at ordinary temperatures such as 0.degree.-100.degree. C. by stabilizing the polymer against the effects of ultraviolet light. At higher application temperatures, rubber, plastics, and such hydrogen-containing halogenated hydrocarbon resins as polyvinyl chloride (PVC), polyvinyl fluroide (PVF) and polyvinylidene fluoride (PVF.sub.2) have been protected from degradation by the use of various types of zeolites. Some patent references say it is important to use zeolites which have been activated by driving off more or less of the contained water of hydration; others say they should be unactivated. Some say the zeolites should be ion-exchanged with monovalent metals like sodium; others say divalent metals like calcium are necessary. Some say at least minimum ion exchange capacity is important; some use two types of zeolites with differing pore size and water content, and still others also require additional retarders to work in conjunction with the zeolites.
However, the patents and publications described above deal with hydrogen-containing resins and not with perfluorocarbon resins such as PFA and FEP. Partially because of the lack of hydrogen, perfluorocarbon resins such as PFA can be used continuously at much higher temperatures than PVF.sub.2 without substantial loss of function, perhaps 260.degree. C. for PFA and 205.degree. C. for FEP versus 150.degree. C. for PVF.sub.2 and PVF, and 80.degree.-120.degree. C. for PVC. While the mechanisms of oxidative and thermal degradation of perfluorocarbon resins may not be completely understood, they do not include to a substantial extent one of the primary mechanisms in PVC, PVF and PVF.sub.2, dehydrohalogenation, since the perfluorocarbon resins do not include hydrogen in the polymer.
The predominant mechanisms of degradation in perfluorocarbon resins may include formation of peroxides and chain-cission, leading to lower molecular weight species. Even perfluorocarbon resins tend to have functional end groups such as carboxylic acid groups. These can complicate any study of the degradation mechanisms, especially where the molecular weight of the resin decreases during the degradative process. Considering the higher temperature capabilities of PFA and FEP compared to PVF.sub.2, one cannot forecast what will happen with the perfluorocarbon resins from what has been tried with PVF.sub.2, especially when applying the perfluorocarbon resins to uses at temperatures higher than the highest at which PVF.sub.2 can be used.
Melt processible fluorine-containing resins, including polymers of tetrafluoroethylene such as with hexafluoropropylene, known as FEP, and also chlorotrifluoroethylene (CTFE) and PVF, but not including polytetrafluoroethylene homopolymer itself, are the subject of U.S. Pat. No. 4,248,763--Yoshimura, et al. (Feb. 3, 1981). That patent uses a combination of an amine antioxidant, an organosufurous compound, and at least one of carbon black and iron, nickel or cobalt to obtain improved thermal stability in the melt processible fluorine-containing resin. Although some of these resins are perfluorocarbon resins, others contain hydrogen. The maximum use temperatures for the hydrogen-containing polymers are not as high as those for PFA and FEP, and several of the cited additives tend to be consumed rapidly at temperatures below the maximum use temperatures for PFA and FEP.
Coating compositions containing PTFE, FEP, PFA and other perfluorocarbon resins separately or in combination, in formulations suitable for industrial and cookware applications, are known in several U.S. patents, including U.S. Pat. No. 4,252,859--Concannon and Vary (Feb. 24, 1981);
U.S. Pat. No. 4,123,401--Berghmans et al. (Oct. 31, 1978); PA0 U.S. Pat. No. 4,143,204--Fang (Mar. 6, 1979); PA0 U.S. Pat. No. 4,145,325--Vassiliou, et al. (Mar. 20, 1979); PA0 U.S. Pat. No. 4,147,683--Vassiliou, et al. (Apr. 3, 1979); PA0 U.S. Pat. No. 4,150,008--Vassiliou, et al. (Apr. 17, 1979); PA0 U.S. Pat. No. 4,169,083--Vassiliou (Sept. 25, 1979); PA0 U.S. Pat. No. 4,180,609--Vassiliou (Dec. 25, 1979); and PA0 U.S. Pat. No. 4,311,634--Vassiliou (Jan. 19, 1982),
all of which are hereby incorporated herein by reference.
Zeolites are reversibly hydrated aluminum silicates generally containing alkali or alkaline earth metal oxides which sometimes can be ion exchanged for other metals or for hydrogen. A general structural definition is EQU M.sub.x/n [(AlO.sub.2).sub.x (SiO.sub.2).sub.y ].multidot.mH.sub.2 O
wherein M is a cation of valence n, and n is 1 or 2. The ratio of x to y can vary from 1 to a large number, as is known in the art. Zeolites have a framework structure often permitting their use as molecular sieves after removing the water which can leave a void volume (depending on the value of m) of up to 50% with a narrowly defined pore size on the order of a few microns. Zeolites include many naturally occurring minerals and synthetic materials. The class of minerals known as feldspathiods is closely related to zeolites and is included herein in the meaning of the term zeolite. Feldspathoids, including sodalite and ultramarine, are more open in structure with large cavities than feldspars which are anhydrous. Thus, feldspathoids are more closely related to other zeolites than to feldspars.
Ultramarine blue is known as a heat-resistant pigment for use in PVF.sub.2. See Kunststoff-Handbuch, Band XI, p. 409, Carl Hanser Verlag-Munich (1971).